CN111961440A

CN111961440A - Biopolymer thickening agent and preparation method and application thereof

Info

Publication number: CN111961440A
Application number: CN202010863391.5A
Authority: CN
Inventors: 张甲吉
Original assignee: Individual
Current assignee: Individual
Priority date: 2020-08-25
Filing date: 2020-08-25
Publication date: 2020-11-20

Abstract

The invention discloses a biopolymer thickening agent and a preparation method and application thereof, the biopolymer thickening agent is prepared from biogel, suspension and emulsifier, wherein: the weight percentage content of the biological glue in the biological polymer thickener is not more than 60 percent; the weight percentage content of the suspension in the biopolymer thickening agent is not lower than 30%; the balance of emulsifier; the suspension is a mixture of organic bentonite and grease. The biopolymer thickening agent provided by the invention not only has low temperature resistance, can solve the problem of difficult preparation of dispersion liquid under low temperature conditions, but also has the characteristics of heat resistance, salt resistance and rapid dispersion and dissolution, and in addition, the biopolymer thickening agent can be directly used without preparation treatment, can generate a solution with high viscosity and good suspension property even under low concentration, has better lubricating and emulsifying functions, and can be used in a plurality of technical fields of exploration, oil field drilling, printing ink, fire fighting and the like.

Description

Biopolymer thickening agent and preparation method and application thereof

Technical Field

The invention relates to the technical field of industry, in particular to a biopolymer thickening agent, a preparation method of the biopolymer thickening agent and application of the biopolymer thickening agent in the technical fields of exploration, oil field drilling, printing ink, fire fighting and the like.

Background

The related data show that the quantity of petroleum recoverable resources in China is estimated to be 150 hundred million tons, and about 85 hundred million tons of petroleum recoverable resources are discovered and proved to account for 57 percent of the proved degree of petroleum recoverable resources. The part of petroleum resources to be explored are mainly distributed in Tarim, Quercoas, Chauda and Tuoha, and are main successive areas of the petroleum yield in China. Meanwhile, 73% of the resource amount is buried below 5000 meters. The earth has an average earth temperature gradient of 3 ℃/100m and drilling to recover oil in these areas requires high temperature resistant quality drilling mud.

The biogel used for preparing the drilling mud is powder in a conventional state, and generally needs to be dissolved by a solvent and then prepared for use. However, in some low-temperature areas in winter, after the temperature reaches below zero, the conventional biological glue cannot be quickly dissolved in ice water and the viscosity is released to achieve the thickening effect, so that the application of the biological glue is difficult, even part of areas stop drilling and exploration in winter, the construction is stopped, and the construction period and the cost are increased. In addition, conventional biogums are not easily formulated into solutions when used in special environments and are difficult to achieve desired effects, such as when used in offshore drilling, and conventional biogums are difficult to adapt to the salinity of seawater in different sea areas. In addition, in a high-temperature environment with a temperature of 120 ℃ to 150 ℃, such as a deep underground area of more than 3000 meters, the conventional biogel solution has a viscosity which decreases with the increase of temperature, cannot maintain normal thickening and suspending properties, and cannot effectively carry silt and lubricate a drill bit.

Disclosure of Invention

The invention provides a biopolymer thickening agent which can generate high-viscosity dispersion liquid with excellent suspension performance under different environmental temperatures and different salt water conditions, and has the characteristics of low temperature resistance, heat resistance and salt resistance.

A biopolymer thickening agent is prepared from a biogel, a suspension and an emulsifier, wherein:

the weight percentage content of the biological glue in the biological polymer thickener is not more than 60 percent;

the weight percentage content of the suspension in the biopolymer thickening agent is not lower than 30%;

the balance of emulsifier.

Further, the weight percentage of the emulsifier in the biopolymer thickening agent is controlled to be 5% -10%.

Preferably, the suspension is present in the biopolymer thickening agent in an amount of 30% to 70% by weight.

Further, the biogum is one or a mixture of more than two of xanthan gum, welan gum and diutan. Xanthan gum is a biological gum integrating thickening, suspending, emulsifying and stabilizing functions and having excellent performance. Similar to xanthan gum, welan gum and diutan gum are also excellent biogums.

Further, the suspension is a mixture of organic bentonite and grease; the weight percentage of the organic bentonite in the biopolymer thickening agent is 1-5%. The organic bentonite is an inorganic mineral/organic ammonium compound, takes bentonite as a raw material, and is prepared by inserting an organic covering agent through an ion exchange technology by utilizing the lamellar structure of montmorillonite in the bentonite and the characteristic that the lamellar structure can be swelled and dispersed into colloidal clay in water or an organic solvent. The organic bentonite can form gel in various organic solvents, oils and liquid resins, and has good thickening property, thixotropy, suspension stability, high-temperature stability, lubricity, film-forming property, water resistance and chemical stability.

Further, the grease is one or more of mineral oil and epoxidized soybean oil. The epoxidized soybean oil is a chemical product prepared by carrying out peroxidation treatment on soybean oil, is a light yellow viscous oily liquid at normal temperature, has excellent weather resistance and heat resistance, has excellent thermal stability, light stability, water resistance and oil resistance, is nontoxic and can be biodegraded.

Further preferably, the mineral oil is white mineral oil.

Further, the emulsifier is one or a mixture of more than two of sorbitan fatty acid ester, sorbitan oleic acid triester and sorbitan fatty acid ester polyoxyethylene ether. The emulsifier is used as emulsifier, thickener, wax inhibitor and heavy oil wetting resistance reducer in oil extraction industry and other industries. The emulsifier plays a role in water-in-oil and oil-in-water, the particles are suspended and the friction is reduced, and the mineral oil is emulsified and dispersed in water under the action of the emulsifier, so that the lubricating effect is played on the drill bit.

The application also provides a preparation method of the biopolymer thickening agent, which comprises the following steps:

(1) weighing the components according to a proportion, sequentially adding the grease and the emulsifier into a reaction kettle, adding the organic bentonite while stirring, and stirring the suspension until the components are uniformly mixed;

(2) heating the suspension to 60-100 ℃, then adding the biogel into the reaction kettle, keeping the temperature and stirring for 1-2 hours, and then emulsifying the mixture uniformly to obtain the biopolymer thickening agent.

Further, emulsifying the mixture for 1-2 hours by a three-stage emulsification pump during emulsification.

The invention also provides application of the biopolymer thickening agent in the fields of exploration, oil drilling and fire fighting, and in preparation of printing ink and latex paint.

The invention has the beneficial effects that:

1. the invention provides a biopolymer thickening agent applicable to different temperature conditions, which is prepared from biogel, an emulsifier, organic bentonite and grease, wherein the prepared biopolymer thickening agent has low-temperature resistance, can be normally used even at the temperature of minus 20 ℃, and solves the problem that the dispersed liquid of the biogel is difficult to prepare due to water freezing under the low-temperature condition;

2. the biopolymer thickening agent has the characteristics of heat resistance and salt tolerance, shows excellent salt tolerance, thickening property and suspension property in seawater with different components, can be directly used without preparation treatment, and can be used in a plurality of technical fields such as exploration, oil field drilling, printing ink, fire fighting and the like;

3. the biopolymer thickening agent of the present invention has excellent lubricating and emulsifying effects, and can produce a high viscosity, good suspendability, biopolymer thickening agent for biogums even at low concentrations.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.

It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.

Example 1: preparation of biopolymer thickener containing 30% of biogel

The embodiment provides a biopolymer thickening agent, and raw materials for preparing the biopolymer thickening agent comprise the following components in percentage by weight: 30% of biological glue, 60% of suspension and the balance of emulsifier.

Specifically, the biogums include 20% welan gum and 10% xanthan gum.

Specifically, the suspension is prepared by dispersing organic bentonite in white mineral oil, wherein the weight percentage of the organic bentonite in the biopolymer thickening agent is 5%.

Specifically, the emulsifier is a mixture of sorbitan fatty acid ester, sorbitan oleic acid triester and sorbitan fatty acid ester polyoxyethylene ether with equal mass.

The preparation method of the biopolymer thickening agent of this example includes the following steps:

(1) weighing the components according to a proportion, sequentially adding white mineral oil and an emulsifier into a reaction kettle, adding organic bentonite while stirring, and stirring the suspension until the components are uniformly mixed;

(2) and heating the suspension to 80 ℃, adding the biogel into the reaction kettle, keeping the temperature and stirring for 2 hours, emulsifying the mixture for 2 hours by using a three-stage emulsification pump, and obtaining the biopolymer thickening agent after uniform emulsification.

Example 2: preparation of biopolymer thickener containing 40% of biogel

The embodiment provides a biopolymer thickening agent, and raw materials for preparing the biopolymer thickening agent comprise the following components in percentage by weight: 40% of biological glue, 52% of suspension and the balance of emulsifier.

Specifically, the biogel comprises 15% xanthan gum and 25% welan gum.

Specifically, the suspension is prepared by dispersing organic bentonite in white mineral oil, wherein the weight percentage of the organic bentonite in the biopolymer thickening agent is 4%.

(2) heating the suspension to 90 ℃, adding the biogel into the reaction kettle, keeping the temperature and stirring for 1.5 hours, emulsifying the mixture for 2 hours by using a three-stage emulsification pump, and obtaining the biopolymer thickening agent after uniform emulsification.

Example 3: preparation of biopolymer thickener containing 50% of biogel

The embodiment provides a biopolymer thickening agent, and raw materials for preparing the biopolymer thickening agent comprise the following components in percentage by weight: 50% of biological glue, 44% of suspension and the balance of emulsifier.

Specifically, the biogel comprises 25% xanthan gum and 25% welan gum, or comprises 25% xanthan gum and 25% diutan.

Specifically, the suspension is prepared by dispersing organic bentonite in white mineral oil, wherein the weight percentage of the organic bentonite in the biopolymer thickening agent is 3%.

(2) heating the suspension to 60 ℃, adding the biogel into the reaction kettle, keeping the temperature and stirring for 2 hours, emulsifying the mixture for 2 hours by using a three-stage emulsification pump, and obtaining the biopolymer thickening agent after uniform emulsification.

Example 4: preparation of biopolymer thickener containing 60% Biogel

The embodiment provides a biopolymer thickening agent, and raw materials for preparing the biopolymer thickening agent comprise the following components in percentage by weight: 60% of biological glue, 30% of suspension and the balance of emulsifier.

Specifically, the biogel comprises 30% xanthan gum and 30% welan gum.

Specifically, the suspension is prepared by dispersing organic bentonite in mixed grease of white mineral oil and epoxidized soybean oil, wherein the weight percentage of the organic bentonite in the biopolymer thickening agent is 5%. Specifically, the greases in this example included equal quality white mineral oil and epoxidized soybean oil.

(2) and heating the suspension to 100 ℃, adding the biogel into the reaction kettle, keeping the temperature and stirring for 1 hour, emulsifying the mixture for 1 hour by using a three-stage emulsification pump, and obtaining the biopolymer thickening agent after uniform emulsification.

In example 4 of the present application, the combination of the biogums may be the following combination: the 60% biogum comprises 20% xanthan gum and 40% welan gum, or comprises 20% xanthan gum, 20% welan gum and 20% diutan.

The biopolymer thickeners prepared in examples 1-4 of the present invention were also tested as follows:

1. salt tolerant viscosity test

(1) Separately, 3.3g of 30% biopolymer thickener, 2.5g of 40% biopolymer thickener, 2g of 50% biopolymer thickener, and 1.67g of 60% biopolymer thickener were added to 358g of synthetic seawater, and stirred for 35 minutes in a vigorously stirred and mixed state by dissolving 419.50 g of sea salt (ASTM D-1141-52) in 9830g of distilled water, and adjusting the pH of the sea salt solution to 8.2 to 8.5 with 0.1N sodium hydroxide and 0.1N hydrochloric acid after stirring and dissolving in a high-speed stirrer controlled to 11000. + -. 200 rpm.

(2) The solution temperature was adjusted to 25. + -. 0.5 ℃ and the viscosity values at 3rpm, 6rpm, 100rpm, 200rpm, 300rpm, 600rpm were measured using a Fann 35A (f ═ 0.2) viscometer, respectively, using a Brookfield LV viscometer, API viscosity at 1.5rpm on spindle # 1.

The viscosity of the biopolymer thickener prepared in the examples of this application at different stirring speeds is shown in table 1.

TABLE 1 viscosity of biopolymer thickeners at different rotational speeds

2. Temperature resistance test

(1) Respectively adding 5g of 30% biopolymer thickening agent, 3.75g of 40% biopolymer thickening agent, 3g of 50% biopolymer thickening agent and 2.5g of 60% biopolymer thickening agent into 358g of saturated saline (the pH of the saline solution is adjusted to 10.0 by 0.1N sodium hydroxide and 0.1N hydrochloric acid generally), stirring for 30 minutes in a vigorous stirring and mixing state of a high-speed stirrer with the speed controlled to be 11000rmp/min +/-200 rpm, and respectively adding 1 g of anhydrous potassium sulfite to stir and dissolve;

(2) hot rolling the prepared solution in a hot rolling heating furnace at 121 ℃, 130 ℃ and 140 ℃ for 24 hours, adjusting the temperature of the solution to 25 +/-0.5 ℃, and measuring the viscosity values at the rotating speed of 300rpm and the rotating speed of 600rpm by using a Fann 35A (f is 1.0) viscometer;

yield value YP: 2 ^ eta (300rpm) ≥ eta (600rpm) ≥ 16lbs/100ft 2.

Eta (300rpm) refers to the viscosity of the biopolymer thickener at a rotation speed of 300rpm, and eta (600rpm) refers to the viscosity of the biopolymer thickener at a rotation speed of 600 rpm.

The final viscosity of the biopolymer thickener of the examples of this application at different temperatures and different stirring speeds is shown in table 2:

TABLE 2 viscosity of biopolymer thickeners at different temperatures and different rotational speeds

As can be seen from tables 1 and 2, the present invention provides a biopolymer thickener that can be applied to different temperature conditions. The inventor finds that only xanthan gum can meet the yield value of 16lbs/100ft2 after hot rolling at 120 ℃, so when the yield value index required by a customer only meets 120 ℃ and does not need to reach 150 ℃, the biopolymer thickening agent of the invention can meet the requirement by using xanthan gum, and if welan gum or diutan or at least two of xanthan gum, welan gum and diutan are used, a better yield value can be realized at 140 ℃.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.

Claims

1. A biopolymer thickening agent is characterized by being prepared from a biogel, a suspension and an emulsifier, wherein:

the balance of emulsifier.

2. The biopolymer thickening agent of claim 1, wherein the weight percentage of the emulsifier in the biopolymer thickening agent is controlled between 5% and 10%.

3. The biopolymer thickener of claim 1, wherein the biogum is one or a mixture of two or more of xanthan gum, welan gum, diutan gum.

4. The biopolymer thickener of claim 1, wherein the suspension is a mixture of an organobentonite and a lipid; the weight percentage of the organic bentonite in the biopolymer thickening agent is 1-5%.

5. The biopolymer thickener of claim 1, wherein the oil is one or more of a mineral oil and an epoxidized soybean oil.

6. Biopolymer thickener according to claim 5, characterized in that the mineral oil is white mineral oil.

7. The biopolymer thickener according to claim 1, wherein the emulsifier is one or a mixture of two or more of sorbitan fatty acid ester, sorbitan oleic acid triester, and sorbitan fatty acid ester polyoxyethylene ether.

8. A method of preparing a biopolymer thickening agent according to claims 1-7, characterized in that it comprises the steps of:

9. The method of claim 8, wherein the mixture is emulsified for 1-2 hours by a three-stage emulsification pump.

10. Use of the biopolymer thickener according to any of claims 1-7 in exploration, oil drilling, fire fighting fields and for the preparation of inks, latex paints.